Manufacture of new azo dyestuffs



Patented May 14, 1940 UNlTED- STATES- PATENT OFFICE MANUFACTURE OF NEW: AZO nynsrurrs Wilfrid Herbert Cliffe, Blackley, Manchester,

England, assignor'to Imperial Chemical. In-

dustries Limited, Britain a corporation of: Great No Drawing. ApplicationMay 2 1, 1937, Serial No. 144,099. In Great Britain May 26, 1936'- 7 Claims. (Cl; 260-160) This invention'relates to the manufacture of new azo dyestuffs.

This invention has, as an object to produce new azo dyestuffs. A further object is to provide a new method of manufacturing azo dyes. A still further object is to provide .a .new method of dyeing. 1 Further objects will appear hereinafter.

Theseobjectsare accomplished by the following. invention. I-.have found that I can manufacture new azo dyestuffsby tetrazotising. 1- molecular proportion of a diamine of, the. general formula.

where both R and R' are phenylene or alkyl substituted phenylene and R" is alkyl, and coupling with 2 molecular proportions of the same or two different coupling components. e 1

An alternative method'of manufacturing some of'the newdyestuffs is by diazotising 1 molecular proportion of a'nitroamine of the formula and R, R" and R have the significance given above-coupling with. 1" molecular proportion of a coupling component free from diazotisable amino groups, reducing thenitro group of the azo compound'so-obtained, and again diazotising and cou-..

pling with 1 molecular proportion of the same ora different coupling component.

The following examples illustrate but do not,

limit the invention.

Example 1 33 parts of 3:4'-diamino-4-methy1benzoyl-N- ethyl-anilide are dissolved in 62.5 parts'of 36% aqueous hydrochloric acid and 600parts of water and tetrazotised at 5-10? C. with a solution of v17.2 parts of sodium nitrite in l2 5;parts of water. The resulting tetrazo solution is added gradually to an ice-cold solution of 63.6 parts of 1-(4'-sulphophenyl) -3-rnethyl-5-pyrazolqllc, and 60 parts of; anhydrous sodium carbonate in, 500 parts of water. Coupling is rapid and thenew dyestuff so formed is saltedout, filtered off and dried. The new dyestuff issoluble in-water and dyes wool from an acid or neutral bath in reddish-yellow shades of good :lightfastness and very goodfastmess to millingand'washing.

It has the probable formula:

action mixture is stirred at 0-5 C. throughout the addition, After stirring for a further 16 hours, during which time the reaction mixture has been allowed toflrise to rom temperature, the

total mixture is-poureclon to ice and the 3:4- dinitro-4-methylbenzoyl-N-ethylanilide which is thus precipitated isfiltered off and washed i'with Water. By recrystallization from ethanol the hinitro compound is obtained in the form of,pa1e crystals M. P. 1&4? C. By heating with dilute sulphuric caid the dinitro compound may be hydrolysed to give a mixture of 4-nitro-ethylaniline and 3-nitro-4-methyl-benzoic acid.

The dinitro compoundzis readily reduced to the required diamine by means of ironand hydrochloric or acetic acid 'in aqueous or ethanol medium; The resulting diamine when recrystallized from aqueous ethanol gives white crystals M. P. 158 C. It has the probable formula Example 2 33 parts of the 3:3-diamino-4-methylbenzoyl- N-ethylanilide of Example 1 are tetrazotised as therein described. The resulting tetrazo solution is neutralized to Congo red paper by addition of aqueous sodium hydroxide at 0-5 C. To the neutralized tetrazo solution is added a solution of 17.2 parts of salicylic acid in 5.0 parts of sodium hydroxide and 350 parts of water, followed by addition of parts of anhydrous sodium carbonate dissolved in 150 parts of water. The coupling mixture is stirred at 0-5 C. until the formation of the monoazo compound is complete. A further 30 parts of anhydrous sodium carbonate dissolved in 150 parts of water are then added, followed by a solution of 4.2 parts of the sodium salt of 2-pheny1amino 8 naphthol 6 sulphonic acid. The coupling mixture is stirred until coupling is complete and the new disazo dyestuif is salted out, filtered off and dried. The new dyestufi is soluble in water and dyes wool from a neutral or acid bath in brown shades which have very good fastness to washing and milling. It has the probable formula:

33 paras of 3:4-diaminol-methylbenzoyl-N- ethyl-anilide are tetrazotised as described in Example 1 and the tetrazo solution so obtained is added gradually to an ice-cold solution of 87 parts of the disodium salt of 2-naphthol-6:8- disulphonicacid and 50 parts of anhydrous sodium carbonate in 600 parts of water. Coupling is rapid and the dyestufi so formed is salted out, filtered off and dried. It is soluble in water and dyes wool from an acid or neutral bath in orange shades of good fastness to washing and milling and of very good fastness to light. It has the probable formula: I

ample 1 and the tetrazo solution so obtained is added to an ice-cold solution :of 77 parts of the sodium salt of Z-N-p-hydroxyethylamino-8- naphthol-S-sulphonic acid and 50 parts of anhydrous sodium carbonate in 600 parts of water. Coupling is rapid and a portion'of the new dyestuff so formed separates out of the solution. Salt is added to precipitate the remainder and the dyestuff is filtered off and dried. It is soluble in water and dyes wool from an acid bath brown shades of very good fastness to washing and milling and to light. It has the probable formula:

Ewample 5 49.3 parts of 4:4-diaminobenzoyl-N-dodecylanilide are dissolved in 62.5 parts of 36% aqueous hydrochloric acid and 500 parts of water and tetrazotised as 5-10 C. with a solution of 17.2 parts of sodium nitrite in 125 parts of water. The resulting tetrazo solution is added graduallyto an ice-cold solution of 66 parts of the sodium salt of 2:8-aminonaphtho1-fi-sulphonic acid and 50 parts of anhydrous sodium carbonate in 600 parts of water. Coupling is rapid and a portion ofthe new dyestufi so-formed separates out of solution. Salt is added to precipitate the remainder and the dyestufl is filtered off and dried. It dyes wool from a neutral or acid bath bright shades of red-brown and of very good fastness to washing and milling and to light. It has the probable formula:

S-OH

Example 6 49.3 parts of 4:4-diaminobenzoy1-N-dodecylanilide are tetrazotised as in Example 5 and the tetrazo solution so obtained is added gradually to an ice-cold solution of 7'7 parts of the sodium salt of 2-N-B-hydroxyethylamino-8-naphthol-6 sulphonic acid and 50 parts of anhydrous sodium carbonate in 600 parts of water. Coupling is rapid and the new dyestufi so formed separates out of solution and is filtered off and dried. It dyes wool from a neutral or acid bath brown shades of very good fastness to Washing and mill- 33 Parts Of 'd hy Z0y -N- ing and of good fastness to light. It has the ethyl-anilide are tetrazotised as described in Exprobable formula:

OH I OH H 121311 1? 110432114 1 1 N= ON-COON: N-casn-oH O l -OH HO H H o fill Further examples of dyestufis' obtained according to the invention are given in the following table.

,414 3 and coupling with two molecular proportions of the same or two difierent coupling components.

Diazo component Coupling components Shade on wool 3:4-diamino-4methylbenzoyl-N-ethylanilide.... 2 mols. oi 1-(2:5 dlehloro-y-sulphophenyl)-3-methyl-5-pyrazolone. Yellow. 2 mols. oi l-naphthol-4-su1p Scarlet. 2 mols oi i-naphthyl-aniine Orange. 2 mols. of 2-naphthol-6-Su Reddish orange. 2 mols. of 2-phenylamino-8-naphthol Red-brown. 1 mol. of salicylic acid }Yeuowish red. {1 mol. of l-phenyl-amino mol. of salicylic acid }Orange 1 mol. of 2-naphthol-fi-sulphonic aci 1 mol. of salicylic acid (acid) teen 1 mol. of monoazo compound (p-nitroaniline -v 1:8-amlnonaphthol-3z6-disulphonic acid). 2 mols. of 2-naphthol-8-sulph0m0 acid Orange. 2 mols. of 2-acetylarnino-8-naphtliol-6-si lphonic acid Bright red.

2 mols. f2-Daphth0l-3Z6-dlSl1lpllOI1l0 acid Yellowisli red. 2 mols. of 2:8-aminouaphthol-fi-sulphoinc acid... Red-brown. 2 mols. of l-acefylamliino-ilmaphtliol-El:6-disulphonic acid Bluish-red. 1 mol. of salicy ic sci 1 mol. of 2-naphthol-fizB-disulphomc acid. }Yenw1sh orange- 1 mol. of l-napl'itholi-sulplionic acid }scm let' 1 mol. of 2-naphthol-3z6-disulphomc acid... 2 mols. oi inonoazo compound acid Reddish navy blue p-Nitraniline- 1:8-aminonaphthol-3:6-disu1ph0nic acid 2 mols. of 1- (4-sulphophenyl)-3;mcthyl-5-pyrazolone Yellow. 2 mols. of 2-naphthol-6-sulphonic acid" Orange. 2 mols. of 2-naphthol-6z8-disulplionit} acid... Do. 2 mols. of Z-naphthol-B-sulphonic acid Do. 2 mols. of 2-acctylamino-5-naphthol-7-sulphon c ac d. Reddisli'orange. 2 mols. of 2-acetylarnino-8-naphthol:6-sulphonic acid. Red. 2 mols. of l-naphthol-i-sulphonic acid. Scarlet. 2 mols. of l-naphthol iizfi-disulplhonic acid Do.

2 mols. of l-acetylammo-S-nap thO1-3I61ll5lllph0nl0 Bluish-red. 2 mols. of 2:8-aminonaphthol-6-su1phon1c acid. Red-brown. 1 mol. of 2-phenylamino-8-naphthol-6-sulphonic ac 1 mol. of 2:S-aminonaphthol-3zo-disulphonic acid 1 mol. of salicylic acid acid Bluish-green. 1 mol. of p-nitraniline l:8-aminonaphthol-3zfi-disulphouic acid. 2 mols. of l-(2:5-dich1oro4-sul phophenyl)-3-methyl-5-pyrazolone..- Yellow. 2 mols. of 2 naphthol-8-sulphonic acid Orange. 2 mols. ol 2- naphthol-fiz8-disulphon c Do. 2 mols. of l-naphtli ol-4-sulphonic acid. Scarlet. 2 mols. of l-(4-sulphophenyl)-Il-methyl-5pyrazolone.. Yellow. 2 mols. or l-nflphthOl-l-SUIDIIOUIC acid Scarlet. 2 mols. of 2-N-fl-hydroxyethyl-amino-8-naphthol-6-sulphon1c acid. Yellowlsh-brown. 2 mols. of l-( i-sulphophenyl)-3-methyl;5-pyrazolone Yellow. 2 mols. of 2z8-aminonaphthol-(i-sulphonic acid Red-brown. 2 mols. or 2-naphthol-8-sulphonic acid Orange.

As coupling components I can use, for example, phenols, naphthols, naphtholsulphonic acids, naphthylamines, naphthylamine sulphonic acids, aminonaphthols, their sulphonic acids or N-substituted derivatives, arylpyrazolones, arylpyrazolone sulphonic or carboxylic acids or acetoaceticarylamides. Also I may use as coupling components monoazo compounds such as, for example, the compound obtained by coupling diazotised p-nitroaniline in mineral acid medium with 1 :8-amino-naphthol-3 6-disulphonic acid.

Suitable diazo components may be obtained by nitrating, for example, a benzoylor methylbenzoyl-alkylanilide or a nitrobenzoylalkylanilide and subsequently reducing the dinitro compounds so-obtained either completely to give the required diamines or partially to give the required mononitroamines.

This invention is a valuable advance in the art as it gives new dyestuffs which dye wool from a neutral or acid bath to give dyeings with very good fastness to light, milling, and washing.

As many apparently widely difierent embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined in the appended claims.

I claim:

1. Process for the manufacture of new azo dyestuffs which comprises tetrazotlsing 1 molecular proportion of a compound of the formula 2. The compound represented by the formula:

3. The compound represented by the formula:

on N=N H l .oi

4. The compounds represented by the formula:

in which each E is the nucleus of an azo dyestufl coupling component. 5. The compounds represented by the formula:

l N N-C 0 CH:

and reacting it with a compound represented by the formula:

H fi)('3OHa HO-C r5 7. The process which comprises tetrazotizing the compound represented by the formula:

and reacting it with one or more azo dystufif coupling components.

WILFRID HERBERT CLIFFE.

of the above numbered patent requiring correction as follows:

CERTIFICATE OF CORRECTION. Patent No. 2200mm. May 11;, who.

WILFRED HERBERT CLIFFE.

It is hereby certified that error appears in the printed specification Page 1, second column, lines 29 and 1L1 for "caid" read -acid; line 51+, for "rom" line 58-59;, for "ni-nitro" read dinitro-; page 2, first coiumn, line 58, for "paras" read -parts; lines 55 to 60 inclusive, for

f H OH :1 OH that portion of the formula reading v read and that the 0 8 0 O=S=O said Letters Patent should be read with this correction therein, that the same may conform to the record of the case in the Patent Offi e;

Signed and sealed this 25th day of June, A. D. 19b 0.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents. 

